Treatment of hydrocarbon oils



lNVENT-OR EDWIN r- NELSON BY? 3g ATTORNEY ot. 26, 1937. E. F. NELSON Y TREATMENT OF HYDRQCARBON OILS Filed Aug. 14, 19:53

Patented Oct. 26, 1937 n PATENT oFFlcEV A2,096,820 Y TREATMENT or HYDRocARBoN oms vEdwin F. Nelson, Chicago, llllgassignor to Universal Oil Products Company, Chicago, Ill., a v corporation of Delaware Application August 14, 1933, Serial No. 685,065

1 claim. V(o1. 19e- 96) 'I'his ap-plication is a continuation in part of my application Serial No. 490,471, filed October 22,1930.

This invention relates more particularly to imt5 provements in treating fractionated hydrocarbon vapors. f VAThe4 present invention provides a method for the treatment of hydrocarbon vapors from any distilling system, particularly systems from which '10 motor fuel forms the main or one of-the major finished products, and is especially adaptable for use with cracking systems in which the vapors are fractionated and subsequently treated to produce motor fuel.

Specifically the invention comprises treating fractionated hydrocarbon vapors in successive treating elements where they are subjected to the treating action of nely divided adsorbent materials such as contact clays, fullers earth and the like and subjecting said vapors to fractionation followingeach successivey treating stage.

Among the'advantagesl of the present invention maybe mentioned the following. In the treatment of the hydrocarbon vapors, particularly cracked hydrocarbons, with adsorbent material such as fullers earth, the more highly unsaturated hydrocarbons are polymerized to form gum and resin-like materials and in addition, polymerization reactions are initiated causing the formation of higher boiling more or less un- Y stable material. It is also desirable to remove Vthe polymers formed as quickly as possible since the adsorbent earth becomes less eflicient when coated with the polymers and nothing further is to be gained by a continued contact of the polymers with the earth. This is accomplished by the repeated and successive treatments and fractionations such as are described in connection with the present invention. Another result of the invention is the improvement of the quality of the product and the yield by relatively short time contact of the vapors undergoing treatment with the adsorbent earth or clay, the polymerization products, gums and resins being formed being separated after each stage of treatment as well as in the subsequent fractionations and in addition the unstable intermediate products of the treatment are removed during the fractionation steps. Specifically, the fractionation following the treating step completes the removal of deleterious polymers or intermediate products thereof from the vapors before they are subjected to the succeeding treatment with the clay. 'This results not only in an improved product and yield but in the prolonged life of the adsorbent earth or clay before regeneration is required and a longer cycle of treatment with the resultant economies. n

v In the single drawing a diagrammatic view of K one form of apparatus suitable for carrying out 5 `my invention is shown.

Referring more in detail tothe drawing, indicates a fractionating column which may be part of a distilling system or a cracking system from which hydrocarbon vapors to betreated are supl0 Y for the purpose of separating gum forming or 20 y other'deleterious polymerization products from the desired products; The partially treated vapors then pass'throi'ighY line I0 and valve II to further/treatment in treater I2 in which the vapors are subjected to further treatment of the 25V same nature as that obtained in treater 6. VVapors from treater I2 pass through line I3 and valve I4 to be subjected to further fractionation in fractionating column I5 to effect the separa- Vtion of polymerization products or anyother 30 harmful materials from the vapors. The nally treated vapors from fractionating column I5 may pass through line I6 and valve I1 to condenser I8 where theyare subjected to condensation and cooling, the products passing through lineI I9 and 35 valve 20 to be collected in receiver 2l. Condensed distillate may be withdrawn from receiver 2I' through line 22 and valve 23. Uncondensed vapors and gas may be released from the receiver through line 24, controlled by valve 25. Reflux condensate from fractionating column I may be withdrawn through line 26, controlled by valve 2l, and in case thesystem is operatedin conjunction with a cracking process this reflux condensate may preferably be recycled tov the. 45

cracking system forV reconversion. Heavy polymerization products and the like formed within treaters 6 and I2 may be removed therefrom through line 28, controlled by valve 29, and line 30, controlled by valve 3|, respectively. Heavy gum forming polymerization products and other deleterious materials separated from the vapo-rs in fractionating columns 9 and I5 are removed from the respective zones throughrline 32, controlled by valve 33 and line 34, controlled by 55 valve 35. rritmici withdrawn from any or au of Vsystem or, tion with returned to any desired portion of the cracking VsystemV for further treatment and/orreconver- Y sion. For example, any or all of these products may be` returnedby Well "known means, (not shown) -to'fractinating column I, there combining with the reux condensate and passing therewith through line 26 and valve 21 to the heating element of the cracking system for reconversion.

It will be understood that anyrof the various well known forms of fractionating devices lsuch as packed or bubble towers,Y columns with perforated 'Y L pans or the like may be employed for theV fractionating columns I, 9 andjISV and'that any well known form of treating Yelement capable of per- VVforming .the desiredkfunctionsV may be utilized'lv for treaters Iand-V I2. Itwill alsofbe understood thatthe-same form or diflerentformsv of apparatus may be used for the variousrfractionating lden Y vices and treaters of the system. The exact form orconstruction of thegvarious elements of the system is nota partof the scope. A Y 1 Although two'rtreating stages following fractionating column `I are-illustrated and described a greatervnumber of sirnilarV treating stages may Ybe used and may be followed, if desired, by subsequent treating methods applied to either the va- Dors or'the distillate condensed therefrom,-or both. Subsequent treating methods of a. differ- `entnature dornot, however, form anyY part of the present inventionexcept'in combination. u`As aspecic example Vof the `operation of Vthe Y process of the Vpresent invention, cracked Vvapors containing a substantial percentageY of f material boiling within the range of vmoto'rffuelare sub- J'ected tov Yfractionationin column YI and-practically all of the heavier constituents ofthe vapors boilingfabove the rangeof motor fuel are conpresent inventionas it isY ntgdesirable torso limit its broad spirit andV accese@ .f

densed and separated from the lighter vapors. The light fractionated vapors containing some 600 mgm. of gum the copper dish method, are -then subjected to treatment in treater 6 where they are contacted with the `good qualityv adsorbent earth or clay of about to 120 mesh, are thence subjected to Yfractionation in'k column 9 and passed Vin treater I2` through a bedV of about 60 mesh fullers earth. 'I'he mesh of the earth may vary; of course. 'Ihe vapors from treater I 2 are then'subjected to final fractionation in column I5 and thereafter condensedfand collected. Further stages of treatment may also be employed. The treated productshowedv amarked improvement in color stability and-odor after exposure to sunlight as compared with a sample of the material leavingY column I, or which'has-beensubjected to a single treatment only. V'I'he'gum content was reducedto approximately 8 mgm. per 100 cc. with a color of plus 30 Saybolt and onlyv about one pointY drop'rin'color on .exposure tothe arc:orr sunlight in 'the Vusual per cc, as determined byV color stability test, and the end boiling 'point ,Of

the material islowered by about 10 F. over that leaving fractionating column I. 'I'heryieldv of product Within the boiling range of motor fuel is increased, Aas is also the life of the'clay and l the cycle of treatment, compared with single l stage treatment and fractionationonly.

I claim as-my invention: Y 1

Inthe refining o f hydrocarbon Avapors by treatment with' adsorbent earth, thej process.Y which comprises passing fractionated vapors through a body of adsorbent earth of relatively `fine mesh, fractionatingthe vaporsout V015 contact with adsorbentmaterialthereby condensinga portion of the vapors and separating said condensate and deleteriouspolymerization products from the vapor's, passingv the separated vapors through abody of adsorbent earth of coarsermeshthan--said first mentioned body, subjectingthe.-vapors to nal fractionation andr lcondensing the Yresulting separated vapors as a inal` product ofthe process. EDWIN F. NELSON. 

